Journal
DALTON TRANSACTIONS
Volume 49, Issue 36, Pages 12622-12631Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0dt02450c
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Funding
- National Natural Science Foundation of China [21701089, U1630103, 21871203]
- State Key Laboratory of Intense Pulsed Radiation Simulation and Effect [SKLIPR1715]
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Four coordination polymers (CPs) Mn-TMPP (1), Zn-TMPP (2), Mn-THPP (3), and Zn-THPP (4) have been synthesized and characterized (H2TMPP = meso-tetrakis (6-methylpyridin-3-yl) porphyrin; H2THPP = meso-tetrakis (6-(hydroxymethyl) pyridin-3-yl) porphyrin). The one-dimensional (1D) chain compound 1 is formed via a head-to-tail connection of the Mn-TMPP unit, wherein the central Mn2+ features a square pyramidal geometry coordinated by four N atoms from the porphyrin skeleton and one additional N atom from an adjacent Mn-TMPP unit. Compound 2 features an octahedral Zn2+ center associated with four N atoms from the porphyrin skeleton to define the equatorial plane and two additional N donors at the axial positions to give a two-dimensional (2D) CP. The 1D chain of 1 and the 2D layer of 2 possess distinctive molecular structures but nearly identical molecular arrangements in their unit cells viewed along all three crystallographic axes. By contrast, Mn- and Zn-based CPs 3 and 4 supported by the THPP ligand share both identical molecular connectivities and crystal packing. In 3/4, each Mn/Zn center is chelated by four N donors of the porphyrin interior to define the equatorial plane of an octahedron, whose axial sites are occupied by two alcoholic OH groups from a pair of trans-located pyridinemethanol moieties. The third-order nonlinear optical properties of 1-4 investigated using the Z-scan technique at 532 nm revealed reverse saturable absorption and self-focusing effects for all four CPs, with hyperpolarizability values (y) in the range 1.42 x 10(-28) esu to 7.64 x 10(-28) esu. These high y values are comparable to the best porphyrin-based molecular assemblies, demonstrating potential for these materials in optical limiting applications.
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